Paper making



Jan. 30, 1934. Q l, GESSMANN l 1,944,886

PAPER MAKING Filed April 6, 1933 mgm yPatented Jan. 3l), 1934 y UNIT-ED,STATES PATENT voI-trc'ie dence, R. I., by Anna M. D. Goessmann,executrix, Brooklyn, N. Y. v

i Application April s, 193s. .serial no. 664,811 27 claims. (Cl. 154-2)This invention relates to the art of paper making and has forits objectV the production of a dur-..,`

able, horn-like material from absorbent pulp paper', by xingtherein.desirable added colloidal protein matter.

The present application is a continuation in- It is one of the objectsof the invention that the added matter shall be so united with theoriginal stock that the resultant mass is integral and homogeneous.

Briefly stated the process consists in impregnating raw stock paper in aheated bath prepared from colloidal protein matter and a suitablesolvent; rolling the initially treated paper on a lamination drum ormandrel until the desired number of laminations is attained; squeezingout excess of the added matter; jellifying the colloid in the paper;treating the resultant mass with a fixing or coagulating agent whichrenders the colloid matter insoluble; and drying the final product in acool, dry or heated atmosphere without extraneous pressure. If the nalproduct is to be in tubular form the product is preferably dried on themandrel, but if the nal product is to be in sheet form it is slit andremoved from the drum preferably before drying and is then pressed atand dried.

It will be seen by the above terse description that a soluble colloid isfirst added to the raw stock, then jelled so as to anchor the solublecolloidal matter, then rendered insoluble therein, and then the wholemass dried.

In the drawing, which forms apart of this specification, are showndiagrammatically means for carrying out the steps of the process.

Fig. 1 is a diagrammatical representation of a heated impregnating bathand means for passing therethrough the paper to be treated, the samebeing shown in vertical longitudinal section;

Fig. 2 is a diagrammatical representation of the chilling and fixingbath with the roll ofI im- CTI pregnated paper in positiontherein, thesame being shown in section;

Fig. 3 is a diagrammaticalsketch showing segments ofthe impregnated andxed lamination of paper-cut from the roll on which it `has been formed;

Fig. 4 is adiagrammatic view'similar to'Fig. 1, showing a modicationv ofthe process; and

Fig. 5 is a. diagrammatic view in vertical section, showing a fixingbath in which tubular stock is being fixed.

In the drawing, the reference numeral 10 indicates an impregnatingassembly comprising a bath 11 fitted over a tank 12, which tank isadapted to contain a suitable heating medium 13. 'If 70 desired thistank 12 may be mounted onsupports 14. The bath 11 contains animpregnating medium 15 of colloidal protein matter, such as glue,gelatine, casein, dried blood, albumen, or other nitrogenouscolloiddissolved in water, or any other suitable solvent, and preferably usedhot. f

4The assembly-also includes means, not shown, for supporting a roll ofraw stock paper 17, such as Wood pulp paper, rag paper, or such otherkind of paper as is adapted to absorb a relatively large amount ofmoisture.

The paper is fed through the.bath 15 by being passed over a guide roller18 and under immersion rollers 19 and 20, thence over the enlarged 85guide roller 21, which also serves to express a goodly quantity of theexcess of the impregnating fluid which adheres to the stock. The freeend of the stock is secured to the laminating cylinder 22, which isdriven by drive rollers 23 90 and 24 actuated by suitable means, notshown.

The laminating cylinder which is first covered with parain impregnatedpaper, or other suitable non-adhesive covering, rests on rollers 23 and24, and as the stock is wound on said cylinder a major part of theimpregnating uid is squeezed out of the stock. The stock is wound onthis cylinder until the desired number of laminations is attained. 'Ihenthe web of paper is severed and cylinder 22 with the paper thereon 100is removed bodily and transferred to a chilling and xing bath 25 whichconsists of a tank 26 having open bearings 27 at each end thereof andadapted to receive the axle 28 of the lamination cylinder.

' Tank 26 may be mounted on supports 29, if it is sodesired. Tank 26contains a chilling bath 30 which consists of such a solution of suchcongealing agent as cold water or cold brine, or agents best adapted tocongeal an'd render jellylike the particular colloidal protein matterbeing held in suspension in the impregnating tank.

'I'he congealing bath may be cold water alone or a cold solution ofsalt, alum, formaldehyde, paraldehyde, chromates, di-chromates, -orother suitable coagulent medium and this chilling bath is maintained ata temperature of about 45 degrees Fahrenheit during the chillingoperation which takes place immediately after the lamination iscompleted. 'I'he result of this cooling in the presence of a coagulantis to form a jellylike mass of coagulated colloid imbedding the fibersof the stock. To render this jelly-like material insoluble, it may betreated with chrome alum, tannin, dichromate of potash, formaldehyde, orany other suitable fixing agent simultaneously with congealing. Inpractice the above named fixing agents are addeddirectly to the coolingbath. It it obvious however, that the fixing or coagulating maybeeffected by removing bodily the laminated paper and the cylinder onwhich it was formed from the congealing bath to a new bathconsisting'solely of the desired coagulating o xing agent and its propersolvent.

. The combination cooling and fixing step may be done in the same tankand at the same time. in an already prepared stock solution of fixingchemicals such as formaldehyde, etc.. as described above, dissolved inwater,made up in volume and used cold over and over again. In thestandard stock bath the fixing agent is dissolved in the cold watersolution.

Instead of chilling and thereby jelling the colloid carried by the paperin the fixing bath it may, as stated above, be chilled in a separatebath, in which case it is not necessary to chill the fixing bath belowordinary room temperature, although preferably the temperature of thefixing bath should be kept under degrees Fahrenheit. Instead of jellingthe colloid in Aa bath, the laminated product may stand in the open airfor a while before fixing, until the colloid is at least partiallycoagulated by cooling and partial evaporation of moisture so as to forma homogeneous mass permeating the lamin and bonding them together. Aswill be pointed out more specically hereinafter the jellifying step may.in part, at least. actually precede lamination of the paper. It will beobvious that it is not necessary to use a liquid flxing bath but agaseous fixing agent may also be used. v

When properly fixed the cylinder of laminated paper 31 is cut throughparallel with the axis of the cylinder, as indicated in Fig. 3,Asomewhat attened out and dried in the presence of heat and thencompletely flattened. preferably under pressure. If the chilled bath isused separate from the fixing bath the sheet may be out through parallelwith the axis ofthe cylinder as indicated in Fig. 3 immediately afterchilling. These freed sheets. are at once placed in the fixing bath tolsoak and after fixing are dried and flattened as described. It isobvious that one or more cuts may be made in the cylinder of paper r inremoving it from its forming cylinder.

It is within the purview of this invention to employ cut sheets insteadof roll paper in carrying out the invention,v the essence of which isimpregnating paper stock with a solution of colloidal matter`solidifying the colloidal matter, fixing the ,colloidalmatten and thendrying the treated mass.

f axis if so desired.

It is also within the purview of this invention to employ pressure inthe nal drying operation, although it has been found that the amount ofwater and colloidal matter absorbed by a ton of raw stock producessuicient pressure in coming down to dryness, due to pulling and drawingeffect of the shrinking force, to causethe resultant indurated mass toshrink to approximately of its original thickness, or in other Words, itloses by this process one-fifth of its original ber thickness. This hasbeen accomplished byincreasing the density or specific gravity of apaper mass from .809 sp. gr. to 1.192 sp. gr. or 50% Without mechanicalpressure.

The resultant product is a hard, horn-like and waterproof materialsomewhat like the hard ber, vulcanized, or zinc "chloride lpaper incommon use. Paper produced by the present process has no. tendency'tosplit at the edges, is unusually tough, and is produced at much lesscost than other hard ber papers: Whereas the old processes require Weeksto produce the nal product, the present process is completed in a fewdays.

The process diagrammatically represented in Fig. 4 is quite similar tothat described above. However the web of paper is not submerged in thebath but is iloated on the surface of the colloidal solution so that itwill not pick up a large excess .of the solution, also, at least apartial jelling is eected just prior to the lamination step. Thecolloidal solution 34 (Fig. 4) is containedin a tank 35 provided with ajacket 36 containing a suitable heating medium 37. A web 38 of raw stockpaper taken from a roll 39, passes over a roller 40 and thence under apair of flotation rollers 41 which press the paper against the surfaceof the colloidal solution. The -otation rollers are supported on arms 42pivotally mounted on the tank 35 and lateral arms 43 fixed to the arms42 carry set screws 44 which bear against the upper edge of the tank 35.These set screws determine the depth at which the rollers will besupported in the tank and they are adjustable to allow for Variations ofliquid level so that the web may be maintained in a floating conditionon the surface of the solution. The paper is very absorbent and althoughonly the under face thereof is in contact with the. solution, the latterthoroughly permeates the web to the upper face thereof.

The web 38 on emerging from the tank passes under a scraper 45 and overanother scraper 46 so that excess solution will be removed and the webwill retain only the amount that is actually absorbed in the body of thepaper. The'scrapers are adjustable about a common center to regulatetheir scraping effect upon the web and to Vary the tension on the web asit passes on to the lamination mandrel. Suitable means, such asindicated at 4'7 may be provided for fixing the Scrapers at any desiredsetting.

The web is laminated on a mandrel 50 which is supported on and driven bya pair of rollers 51 just as is the drum 22 on the rollers 23 and 24( Inmaking tubular stock however the diameter of the lamination drum ormandrel is usually much smaller than that employed in making sheet stockand consequently a pressure roller 53 is adapted to bear down upon themandrel 50 or the lamin thereonso as to furnish silicient traction for1,944,886 v 3 the rollers 51 to rotate the mandrel' and wind theWhile-it is desirable to coat the drums or man- Between the Scrapersandthe lamination drum or mandrel isa pair lof conduits 57 disposedrespectively on opposite faces of the web. Air is pumped through theconduits and directed in jets against the web. The drying and coolingeffect of these air jets causes an initial partial jelling of thecolloidal matter so that it becomes tacky and bonds the lamin together.

After a suicient number of lamina: have been wound up on the mandrel theweb is severed, and the mandrel is removed. While the mandrel may beplunged immediately into a chilling and fixing bath it i-s preferable tolet it-stand 4for a while to permit a more thorough anchoring of theco1- loidal matter in the laminated mass. The tubes of laminated fiberare then plunged into a fixing bath to' render the colloidal matterinsoluble, and thereafter they are allowed to 'dry withoutv extraneouspressure. Fig. 5 illustrates a tank 50 filled with a fixing solution 61in which a-number of lamination tubes 62'are immersed. The tank isprovided with suitable means for keeping the fixing solution at thedesired temperature particularly in summer time. As shown in the drawinga coil of pip`e 63v is provided in the tank through which a coolingmedium may be circu lated when desired. I

The lamination tubes may be removed from the mandrels either beforefixing or after fixing.,

Preferably however they are retained on the mandrelsthroughout theprocess and ntil they are nearly or quite dry. This procedure not onlyinsures even drying so that the finished product is free from distortionor warping, but it also results in a denser product. In drying, thelaminated mass shrinks and grips the mandrel very tightly, vproducing atension that is far greater than that which can be obtained in windingthe web on the mandrel. `This drying under high tension results in adenser product than can be obtained when ,the tube is dried off themandrel. This densing effect is particularly marked. in the earlierstages of drying because the drying proceeds from the outside of thetube inward. As the outside of the tube nears comtube tends to draw theinner surface of the tube outward so that it relieves the vtight grip onthe mandrel until eventually the tube may be removed from the mandrelwith comparatively little effort. This same effect of drying undertension may also be used in forming sheet stockfwhen a very dense.product is desired. The Ytreated mass after fixing may be dried withoutremoving it from the lamination drum. After it is dried it is slit intosegments which are softened With steam or moisture and then pressed atand dried.

--It will be understood of course that the preliminary partialpjellingbefore lamination may be used in forming sheet stock as well asinforming tubes.

drels with paraffin or with parafilned paper this may be dispensed withparticularly when the drying is effected on the drum or mandrel. Howeverin such case the surface of lamination cylinder must be of such a naturethat the treated mass will not stick fast thereto. A polished brasssurface has been found satisfactory.

The term raw stock paper used in this specific'ation and in thefollowing claims includes any paper that is notcalendered or that doesnot contain a filler other than glue which would prevent absorptionofthe nitrogenous colloid employed in my process.- y

Minor changes may be rmade in the physical embodiment of the inventionor in the steps of the process without departing from the spirit andlscope of the invention.

What is claimed:

1'. The processr of' making indurated paper which consists inimpregnating raw stock paper with @nitrogenous colloid, immediatelyforming laminations of such impregnated stock prior to solidication,chilling such laminated stock, treating such chilled, impregnated andlaminated stock with a fixing agentto render the colloid insoluble, anddrying the resultant mass.

2. The process of making indurated ber which consists in immersing rawstock paper in a nitrogenous colloid bath, immediately forminglaminations of the raw stock paper after being so immersed beforesolidification, chilling such laminated stock to solidify absorbedcolloid, immersing such chilled, laminated stock in a fixing bath torender such solidified colloid insoluble, and drying the resultant mass.

3. The process of making indurated fiber which consists of immersing rawstock paper in a heated nitrogenous colloid bath, immediately forminglaminations of the raw stock paper after being so immersed beforesolidication, chilling such laminated stock-'to solidify absorbedcolloid, immersing such chilled laminated stock in a fixing bath torender such solidified colloid insoluble, and drying the resultant mass.l

4. The process ofmaking indurated fiber which consists in treating raws'tock paper with a nitrogenous colloid, immediately forming laminations`thereof on a non-adhesive lamination base, solidichilled colloidinsoluble, anddrying the resultant mass.

5. The process of making indurated fiber which consists in immersing rawstock paper in' a heated nitrogenous colloid bath, immediately forminglaminations of the raw stock so treated, expressing excess of absorbedmatter, immersing the laminated raw stock in a chilling bath, immersingthe chilled raw stock `in a fixing bath, and drying the resultant massin the presence of heat.

6. The process of making indurated fiber which consists in immersing rawstock paper in a nitrogenous colloid bath, immediately forminglaminations of the raw stock so treated, expressing excess of absorbedmatter, immersing the lamience of heat.

7. The processof making indurated fiber which consists in immersing rawstock paper in a heated nitrogenous colloid bath, immediately forming ylaminations of the raw stock so treated, expressing excess of absorbedmatter, immersing the laminated raw stock in va chilling bath mainwhichconsists in immersing raw fiber stock in` tained at 45 F., immersing thechilled raw stock in a xing bath and drying the resultant mass in thepresence of heat. v

8. The process of making indurated fiber which consists in immersing rawstock paper in a heated nitrogenous colloid bath, forming laminations ona coated lamination cylinder of the stock so treated, expressing excessof l absorbed matter, immersing the laminated raw stock in a chillingand xing bath, and drying the resultant mass.

9. The process of making indurated ber which consists of immersing rawstock paper in a heated nitrogenous colloid bath, forming laminations ofthe raw stock so treated on a cylinder covered with a .coveringimpregnated with parafn, expressing excess of absorbed matter, immersingthe lamination cylinder with the raw stock thereon in a chilling andfixing bath, and drying the resultant mass.

10. The process of making indurated fiber which consists in immersingraw stocky iiber in a heated nitrogenous colloid bath, immediatelyforming laminations of the raw stock so treated on a cylinder co'veredwith a covering impregnated with paraffin, expressing excess of absorbedmatter, immersing the lamination cylinder with the raw stock thereon ina chilling and xing bath, maintained at 45* F., and drying the resultantmass in the presence of heat.

11. The process of making indurated fiber a heated nitrogenous colloidbath, forming laminations of such treated raw stock on a cylindercovered with paraffin paper, expressing excess of the absorbed colloid,solidifying the absorbed colloid by immersing the lamination cylinder ina colloid by immersing the lamination cylinder in a chilling bathmaintained at about 45 F., rendering the solidiedcolloid insoluble by.treating the chilled stock with a xing agent, and drying the resultantmass in the presence of heat. l

13. The process of making indurated fiber which consists in immersingraw vegetable ber rstock in a heated nitrogenous colloidal bath, forminglaminations of said vegetable stock on a `cylinder covered with paraflinpaper, expressing excess of the absorbed colloid, solidifying theabsorbed colloid by immersing the cylinder with its laminations in acongealing bath maintained at approximately 45 F., rendering saidcolloid insoluble by treating the laminated 'stock with a xing agent,and drying the resultant mass under pressure in the. presence of heat.

14. The process of making indurated ber which consists in impregnatingraw stock paper with a nitrogenous colloid, immediately winding theimpregnated paper on al form before solidification, treating theimpregnated paper while on the form with a xing agent to render thecolloid insoluble.- and drying the resultant mass while on the form.

15. The process of making indurated ber which consists in impregnatingraw stockl paper with a nitrogenous colloid, immediately winding theimpregnated paper on a form lbefore solidication, chilling theimpregnated paper on the form suiciently to jell the colloid, renderingthe colloid insoluble with a fixing agent while on the form, and dryingthe resultant mass on the form.

16. The process of making indurated ber which consists inimpregnatingraw stock paper with a heated nitrogenous colloid, immediately windingthe impregnated paper on a cylinder beforesolidication, immersing thecylinder with the raw stock thereon in a chilling and xing bath, anddrying the resultant mass on the cylinder.

17. The process of making indurated fiber which consists in impregnatingraw stock paper with a nitrogenous colloid, forming laminations of suchtreated paper prior to solidification of the colloid, jelling thecolloid absorbed by the paper stock, rendering the colloid in thelaminated mass insoluble, and drying the laminated mass.

18. The process of making indurated fiber which consists in impregnatingraw stock paper with anitrogenous colloid, forming laminations of suchtreated paper prior to solidication of the colloid, jelling the colloidretained by the paper, immersing the laminated paper in a liquid xingagent to render the colloid insoluble, and drying the resultant mass.

19. The process of 'making indurated ber with a nitrogenous colloid,partly jelling the colloid absorbed by the paper, immediately forminglaminationsv of such treated paper prior to solidiiication of thecolloid, impregnating the laminated paper with a xing agent to render 1the colloid insoluble, and drying the resultant mass.

20. The process of making indurated ber which consists in impregnatingraw stock paper with a nitrogenous colloid, partly jelling the colloidin the paper, immediately forming laminations of such treated paperprior to the solidification of the colloid, exposing the laminated paperto atmosphere for a predetermined minimum period to further `iell thecolloid therein, impreg- 1 natingU the laminated paper with a xing agentto render the colloid insoluble, and drying the resultant mass.

21. The process of making indurated fiber which consists in impregnatingraw stock paper with a heated solution of nitrogenous colloid, partlyjelling the colloid in the paper, forming laminations of the paper thustreated prior to complete jelling of the colloid, cooling the laminatedpaper to further jell the colloid therein, im-

pregnating the laminated paper withva xing agent to render the colloidinsoluble, and drying I the resultant mass.

22. The process of making indurated fiber 'which consists inimpregnating raw stock paper 105 which consists in impregnating rawstock paper with a heated solution ofnitrogenous colloid, jelling thecolloid in the paper, forming lamir ations of the paper thus treatedprior to complete jelling of the colloid,immersing the laminated mass ina chilled xing bath to complete the jell- 4Q 'ing of the colloid and torender the colloid in soluble, and drying the laminated mass.

y 23. The process of' making indurated fiber which lcbnsists inimpregnating raw stick paper with a solution of nitrogenous colloiplaying M5 Jets of air on the impregnated paper to jell the colloidtherein, laminatingv the paper while its colloid content is still inpartly jellied state, exposing the laminated mass to atmosphere forapredetermined minimum period to further jell the colloid therein,immersng the laminated mass in a x'ng bath to render the colloid contentinsoluble, and dryingthe laminated mass.

24. The process of making indurated -flber which consists in`impregnating raw stock paper with a heated solution of nitrogenouscolloid,

' playing jets of air on the paper to jelly the co1- state, immersingthe laminated massin a chill` ing and xing bath to complete jelling ofthe colloid content and to render the jellied colloid insoluble, anddrying the resultant mass.

26. The process of making' indurated ber which consists in floating aweb of raw stock paper on a heated solution `of nitrogenous colloid,scraping excess colloidal solution from the web, exposing the paper to adraught of air to jellthe colloid retained in the web, laminating theWeb before solidification of the colloid therein, cooling' the laminatedmass' and immersing the larhinated mass in a xing bath to render thecolloid insoluble, and drying the resultant mass.

27. The process of making indurated ber which consists in oating aweb ofraw stock paper on a heatedsolution of nitrogenous colloid, scraping.the web to remove excess of colloid solution picked up thereby,exposing the web to a draught of air to jell the colloid contentthereof,

Winding the Webon a lamination cylinder while the colloid is still injellied state, adjusting the tension of the winding on the cylinder toapre-n determined degree, exposing the laminated paper to atmosphere tocool and further coagulate the colloid content therein, immersing thelaminated paper in a fixing agent to render the colloid ir1 soluble, anddrying the resultant mass.

' ANNA M. D. GOESSMANN,

Eec'utrix for Charles I. Goessmanm Deceased.

